ORIGINAL PAPER

Properties of electrospun PVDF/PMMA/CA membraneas lithium based battery separator

Tusiimire Yvonne • Chuyang Zhang •

Changhuan Zhang • Edison Omollo •

Sizo Ncube

Received: 23 December 2013 / Accepted: 9 May 2014

� Springer Science+Business Media Dordrecht 2014

Abstract Poly vinylidene fluoride:poly methyl

methacrylate:cellulose acetate (CA) at ratios of

100:0:0, 90:10:0, 90:5:5 and 90:0:10 respectively,

were successfully electrospun. These membranes

were mixed to form a 12 wt% solution prepared with

volume ratio 7:3 of DMAc:acetone solvents. These

membranes were then analyzed using differential

scanning calorimetry, scanning electron microscopy,

FTIR, WAXD, pore size, porosity% and electrolyte

uptake (EU)%. It was observed that the best absorption

results were obtained in the presence of CA. The

electrospun membrane at ratio of 90:0:10 was

observed with the highest porosity of 99.1 % and EU

at 323 %. It also had a 43.6 % crystallinity and a

162 �C melting temperature. It was then concluded

that addition of CA improved the separator properties.

Keywords Cellulose acetate (CA) � Poly

vinylidene fluoride (PVDF) � Poly methyl

methacrylate (PMMA) � Electrospinning �Battery separator

Introduction

It is evident that there is continuous research being done

in improving specific electrochemical systems and

introducing new battery chemicals. Usually Lithium

based batteries use micro-porous membranes or non-

wovens separators made from polyolefin (Arora and

Zhang 2004) due to their many advantages. However

polyolefin materials like Poly vinylidene fluoride

(PVDF) have a number of short comings like poor

wettability, electrolyte leakage, low porosity and high

cost. A number of studies have been carried out in order

to improve the properties of PVDF and these have led to

modification methods such as blending, surface coat-

ing, surface grafting, heat treatment, pore filling and

sputtering being used in the production of modified

PVDF (Zhang 2007; Ding et al. 2009; Li et al. 2011;

Zhang et al. 2005; Ma et al. 2013; Takemura et al. 2005;

Liu et al. 2011; Cui et al. 2013). Studies of PMMA and

its properties in lithium batteries have been carried out

(Manuel Stephan and Nahm 2006) and these have led

to PMMA being blended with PVDF. The use of poly

methyl methacrylate (PMMA) as a possible electro-

lyte for lithium batteries was explored by Iljima et al.

(1985), Feuillade and Perche (1975), Appetecchi (1995)

T. Yvonne (&) � C. Zhang � C. Zhang �E. Omollo � S. Ncube

College of Textiles, Donghua University,

Shanghai 210620, China

e-mail: yvonnet_2012@yahoo.com

C. Zhang

e-mail: chuyangzhang@dhu.edu.cn

C. Zhang

e-mail: 109027@mail.dhu.edu.cn

E. Omollo

e-mail: edisonomollo@gmail.com

S. Ncube

e-mail: sizomeister@gmail.com

123

Cellulose

DOI 10.1007/s10570-014-0296-1

and Zhou et al. (2004). Although addition of PMMA in

PVDF brought about an increase in porosity, improved

absorption, low costs (Schneider et al. 2001),

enhanced ionic conductivity and improved elongation

at break, there was a decrease in crystallinity (Li et al.

2011; Ding et al. 2009). This decrease was attributed

to the hindrance by PMMA large side group during the

crystallization of PVDF (Ma et al. 2013; Tomura and

Inoue 1992).

With the growing environmental concerns (Padbury

and Zhang 2011), separators made with or blended with a

biodegradable polymer should be an added advantage to

the search of the ideal LITHIUM battery separator.

Cellulose acetate (CA) is widely used due to its high

strength, high stiffness, low weight and the added

advantage of biodegradability and renewability (Jabbour

et al. 2013a; Tseng et al. 2012). Cellulose based

derivatives have been successfully used in lithium

batteries (Lalia et al. 2012; Jabbour et al. 2013a, b;

Kritzer 2006) for the production of electrodes, separators

or as reinforcing agents in gel polymer or solid polymer

electrolytes (Jabbour et al. 2013a). Cellulose based

derivatives have also been successfully used in alkaline

batteries due to their excellent wettability, low processing

costs, high porosity, good mechanical properties and low

weight (Jabbour et al. 2013a; Zhou et al. 2011). CA based

separators have been successfully studied by Gozdz et al.

(2002), Rosso et al. (2006), Zhang et al. (2012), Ren et al.

(2009), and many others (Lee et al. 2010; Samad et al.

2013a; Lalia et al. 2012; Jabbour et al. 2013b). Therefore

a low cost readily available CA was introduced.

In this study, we investigated the battery separator

properties with the addition of CA. Membranes of

PVDF:PMMA:CA at ratios of 100:0:0, 90:10:0,

90:5:5 and 90:0:10 were electrospun and subjected

to tests. Electrospinning was used to manufacture the

separators because membranes produced using this

technique are often of high surface area, good surface

adhesion, high density pores, and large surface to

volume ratio and the three dimensional structure helps

in retaining liquid electrolyte (Subbiah et al. 2005).

Experimental

Materials

CA granules (MW = 30,000 g/mol, 39.8 % acetyl

content and degree of acetyl substitution of 2.5) were

purchased from Deng Wei Zhangmutou Plastics (China)

while PMMA powder was purchased from Alfa Aesar

China (Tiajin) Co., Ltd., PDVF (MW = 400,000 g/mol,

Kynar 761) was purchased from Arkema, France.

Acetone purchased from Changzhou Chemical Reagent

Co., (China). N,N-dimethylacetamide (DMAc) from

Shanghai Lingteng Chemical Reagent Co., Ltd., (China)

and n-butanol from Sinopharm Chemical Reagent Co.,

Ltd., and Electrolyte (EC/DMC1: 1 (W/W) LiPF6 1 mol/

l) from Zhangjiagang Guotai-Huarong New Chemical

Materials Co., Ltd., (China). All reagents were used

without further purification.

Membrane preparation

Solute mixtures of PVDF:PMMA:CA at weight ratios

of 100:0:0, 90:10:0, 90:5:5 and 90:0:10 were dissolved

into a mixed solvent of DMAc:acetone (7:3 by

volume) with a concentration of 12 wt%. The solu-

tions were stirred at room temperature for 24 h to

ensure a homogeneous mixture and degassed in

ultrasonic cleaner for 2 h to get a uniform solution.

The membranes were then prepared for a typical

electrospining arrangement. The solutions were fed

into the 10 ml syringe using a stainless steel needle of

0.514 mm inner diameter. The spinning rate was

0.8 ml/h under a potential difference of 16 kV gener-

ated at a distance of 20 cm from the cathode needle tip

to a grounded anode aluminum foil collector. The

relative humidity and the atmospheric temperature

were maintained at 60 ± 2 % and 21 ± 1 �C respec-

tively. The membranes were then dried at 60 �C for

24 h in a conventional oven to remove any solvent

residual before further use.

Characterization

Using Nicolet 6700 FTIR spectrometer (thermo Fisher

Scientific Inc.,), the FTIR data was obtained from each

sample and the side groups analyzed to verify the

polymer.

The surface morphology of the membranes was

observed under scanning electron microscopy (SEM)

on a TM3000 Tabletop Microscope Hitachi. The SEM

images were then analyzed using image analysis

software (Adobe Acrobat X Pro 10.1.2.45) to measure

the nanofiber diameters.

The thermal properties of the membranes were

analyzed using differential scanning calorimeter (DSC

Cellulose

123

704 F1 Phoenix, NETZCH. Germany) as described in

ASTM D 3418-03. The heating rate for the DSC

machine was set at 10 �C/min within a range of 50–

200 �C under nitrogen atmosphere. The crystallinity

(Xc) was calculated from heat enthalpies of electro-

spun membranes using Eq. 1.

Xc ¼DHf

DH�f� 100 % ð1Þ

where DHf is the PVDF based electrospun membrane

melting enthalpy (J/g) and DH�f is the melting enthalpy

for 100 % crystalline PVDF and has a value of

104.7 J/g (Li et al. 2011).

The wide-angle X-ray diffraction (WXRD, D/Max-

2550, RIGAKU, Japan) using Cu Ka radiation target,

tube voltage of 45 kV, tube current of 50 mA, scan

rate of 2�/min and the scanning range of 2h from 10� to

90� was used.

Pore size and distribution were obtained using the

automatic porometer (3G, Quantachrome Co., USA).

The samples were cut to a diameter of 25 mm before

analyzing the Pore sizes of the samples in their dry and

wet states. The liquid surface tension of 16.00 dynes/

cm was used for wetting.

Porosity % tests were done using the n-butanol

immersion method as described in ASTM D-2873.

The membrane samples were cut into 2 9 2 cm2,

thickness denoted as h and dry weight denoted Wd

before immersing them in n-butanol for 2 h. Excess

liquid was then carefully wiped off the sample surface

using a filter paper before measuring the weight

denoted as Ww. The porosity (P%) of the samples were

then calculated using Eq. 2.

P % ¼ Ww �Wd

qb � Vm

� 100 % ð2Þ

where qb is the density of n-butanol and Vm is fiber

membranes volume.

Electrolyte uptake measurements

For each membrane three samples were cut into discs

of 19 mm diameter. The dry weight measured and

denoted as Wo. The samples were then immersed into

the electrolyte solution for 3 h. Using a filter paper,

excess liquid was carefully wiped off the sample

surface of the sample and the weight was then

measured and denoted as W1. The electrolyte uptake

(EU)% was calculated using Eq. 3.

EU ¼ W1 �W0

W0

� 100 % ð3Þ

Results and discussions

SEM

The surface morphology of the electrospun blended

membranes was done using the SEM and the results

are shown in Fig. 1.

It was observed that with an increase in PMMA

content resulted in an increase in the diameter of the

produced nanofibers as shown in Fig. 2. However

addition of CA content resulted in fibers with a reduced

diameter as shown in Table 1. The highest and lowest

nanofiber average diameters were as 0.95 lm at

100:0:0 and 0.56 lm at 90:0:10 respectively. The

average nanofiber diameter and nanofiber distribution

are important factors in electrospun membranes.

FTIR

PVDF was identified as 1,178 cm-1 at C=F stretching

vibration strength (Li et al. 2011; Liu et al. 2011) as shown

in Fig. 3. This vibration was gradually strengthened to

1,182, 1,179 and 1,181 cm-1 in PVDF:PMMA:CA with

ratios of (b) 90:10:0, (c) 90:5:5 (d) 90:0:10 respectively.

PMMA and CA were both identified by C=O side

group. CA was identified as 1,748 cm-1 at C=O

stretching vibration observed in the CA granules (e).

At a ratio of 90:0:10 (d), C=O stretching vibration

shifted to 1,753 cm-1 due to the interaction with

PVDF. With addition of PMMA in the ratio 90:5:5,

C=O was shifted to 1,731 cm-1. This was because

C=O stretching vibration is also found in PMMA (Li

et al. 2011; Cui et al. 2013). PMMA was identified by

C=O presence at a vibration strength 1,729 cm-1 in

the ratio 90:10:0.

The above observations indicate that there were a

molecular level interactions between the polymers that

were present in the electrospun PVDF:PMMA:CA

membranes (Li et al. 2011).

DSC

As shown in Fig. 4, with the presence of PMMA and

CA there was a reduction in both the melting

temperatures (Tm) and crystallinity% as summarized

in Table 1.

Cellulose

123

The decrease in the Tm due to the presence of

PMMA was attributed to the hindrance of PVDF

crystallization due to the presence of the large group

CH3OCO– in PMMA chains (Ding et al. 2009; Ma

et al. 2013). The highest melting temperature for the

blended membranes was recorded as 161.8 �C at a

PVDF:PMMA:CA ratio of 90:0:10. This same blend

ratio showed the highest percentage of crystallinity of

43.6 %.

It was suggested that crystallinity does not have to

be modified, or only rarely modified for immiscible

blends (Bauduin et al. 1999). Therefore the slight

decrease in Tm in this study may be due to the high

immiscibility between PVDF and PMMA as com-

pared to that between PVDF and CA as well as the

large group side group found in PMMA. Low crystal-

line membranes are known to be beneficial in during

absorption.

WAXD

Figure 5 shows WXRD patterns for electrospun

PVDF:PMMA:CA membranes. It has been proved

that PVDF can exhibit five different polymorphs (a, b,

c, d and e) depending on the processing conditions

(Zheng et al. 2007). In Fig. 6, a very strong diffraction

peak for (a) is PVDF observed at 2h of 20.8�,

corresponding to 110 and 200 reflections of b. Other

membranes registered weak diffraction peaks at 36.6�and 41.7� related to 201 and 111 reflections of b phase

(a)

X 10k

(b) (c) (d)

X 10kX 8kX 8k

Fig. 1 SEM showing the surface morphology of PVDF/PMMA/CA at ratios of a 100:0:0, b 90:10:0, c 90:5:5 and d 90:0:10

0 400 800 1200 1600 2000 24000

20

40

60

80

100

120

Cou

nt

Fiber Diameter (nm)

(a)

0 200 400 600 800 1000 1200 1400 1600 18000

20

40

60

80

100

120

Cou

nt

Fiber Diameter (nm)

(b)

0 400 800 1200 1600 2000 24000

10

20

30

40

50

60

Cou

nt

Fiber Diameter (nm)

(c)

0 200 400 600 800 1000 1200 1400

0

10

20

30

40

Cou

nt

Fiber Diameter (nm)

(d)

Fig. 2 Fiber distribution graphs of PVDF/PMMA/CA at ratios of a 100:0:0, b 90:10:0, c 90:5:5 and d 90:0:10

Table 1 Data summary of PDVF/PMMA/CA membrane

PVDF:PMMA:CA Tm (�C) Melting

enthalpy (J/g)

Crystallinity (%) Average pore

size (lm)

Average fiber

diameter (lm)

Porosity (%) EU (%)

DSC WAXD

100:00:00 164.40 49.80 47.60 41.30 1.88 0.95 88.30 275.20

90:10:00 160.30 38.40 36.70 35.12 2.04 0.82 93.00 277.90

90:05:05 160.50 43.80 41.80 32.86 1.29 0.89 94.20 314.70

90:00:10 161.80 45.60 43.60 45.10 1.60 0.56 99.10 323.40

Cellulose

123

respectively (Kim et al. 2011). This dominance of b in

the electrospun membrane was attributed to the

disentanglement and parallel packing of polymer

chains creating orientation of the chains along the

fiber axis (Cui et al. 2013a).

There was a dominant peak that reflected bcorresponding to 110 and 200 in PVDF. Any addition

of PMMA and CA into the membrane did not cause a

position change in the major PVDF diffraction peak.

This indicated that there was no change in the crystal

structure of the electrospun membranes. Although

there is no change in crystal structure, the polymer

orientation and rearrangement of the crystalline state

was verified by the degree of crystallinity as shown in

Table 1.

Porosity and EU%

Porosity is important as it provides a reservoir for liquid

electrolyte in batteries. The three-dimensional network

structure of electrospun membranes enables easier in

penetration of liquids and thus absorption (Li et al.

2011). Porosity and EU% absorptions of the electrospun

membranes were observed to increase with addition of

PMMA and CA as shown in Figs. 6 and 7. The increase

in the porosity due to the presence of PMMA was

4000 3500 3000 2500 2000 1500 1000 500

% T

rans

mitt

ance

Wavenumber (cm-1)

(a) PVDF: PMMA:CA at 100:0:0 (b) PVDF: PMMA:CA at 90:10:0 (c) PVDF: PMMA:CA at 90:5:5 (d) PVDF: PMMA:CA at 90:0:10 (e) CA granules

(a)

(b)

(c)

(d)

(e)

C=O CF2

Fig. 3 FTIR graphs showing chemical groups of electrospun

membrane

60 80 100 120 140 160 180 200

(a) PVDF: PMMA:CA at 100:0:0 (b) PVDF: PMMA:CA at 90:10:0 (c) PVDF: PMMA:CA at 90:5:5 (d) PVDF: PMMA:CA at 90:0:10 (e) CA granules

Hea

t flo

w

Temperature ( C)

(e)

(d)

(c)

(b)

(a)

Fig. 4 DSC thermograms of electrospun membrane

0 20 40 60

Inte

nsity

(a) PVDF: PMMA:CA at 100:0:0 (b) PVDF: PMMA:CA at 90:10:0 (c) PVDF: PMMA:CA at 90:5:5 (d) PVDF: PMMA:CA at 90:0:10

Two-Theta(deg)

(a)

(b)

(c)

(d)

Fig. 5 WAXD patterns for electrospun membrane

100 0 0 90 10 0 90 5 5 90 0 100

20

40

60

80

100

PVDF: PMMA: CA membranes

Por

osity

(%)

88%93% 94%

99%

Fig. 6 Porosity of electrospun membrane

Cellulose

123

attributed to the large increase of amorphous regions

(Ma et al. 2013) as well as the increase in the surface area

(Li et al. 2011) attributed into the decrease in the average

nanofiber diameters of respective membranes. The

increase in porosity due to the presence of CA was

attributed to the absorption properties of cellulose based

membranes (Lalia et al. 2012; Jabbour et al. 2013a;

Zhang 2007; Mu et al. 2010).

According to Table 1, there was simultaneous

increase in porosity and electrolyte uptake of the

membrane. The highest values were observed within

the membrane with the highest CA weight ratio. The

affinity of the electrolyte to the CA groups is a very

important property for liquid lithium batteries.

Increase in EU% uptake in the presence of PMMA

can be explained as the electrolyte affinity of PMMA

that capture large amounts of liquid electrolyte (Cui

et al. 2013a) with contact.

There was an increase in EU% with the presence of

PMMA and CA as shown in 7. With an increase in CA

wt%, there was an evident increase in EU% from 315

to 323 % at a ratios of 90:5:5 and 90:0:10 respectively.

Increase of EU% due to the presence of CA was

attributed to the absorption properties of cellulose

based membranes (Lalia et al. 2012; Jabbour et al.

2013a; Zhang 2007; Mu et al. 2010). This also

explains the increase of porosity%.

Pore size

Membranes can easily absorb large amounts of

liquids. However, with large pore openings, these

liquids can easily be lost while removing the excess

liquids with filter paper (Kim 2005). This means that

high absorption of liquids does not mean high

retention of these liquids when the pore sizes are

large. This explanation should be true in the case of

90:10:00, where the pore size of 2.04 lm was the

highest registered. However due to the PMMA affinity

to liquids, there was substantial amount of retained

liquids as compared to 100 % PVDF with a lesser pore

size of 1.88 lm. Increase of absorption percentages in

both porosity% and EU%, regardless to the fluctuating

pore size was due to liquid affinity of both PMMA and

CA (Cui et al. 2013a; Mu et al. 2010).

Conclusion

Different weight ratios of PVDF:PMMA:CA mem-

branes were successfully electrospun. Melting mor-

phologies were shown to reduce with addition of

PMMA and CA, however the highest Tm of blended

membrane was shown at a ratio of 90:0:10 at 161.8 �C.

Crystallinity percentage in the electrospun membranes

were also observed at the weight ratio of 90:0:10 at

43.6 and 45.1 % shown by DSC and WAXD data

respectively. There was an increase in porosity and

electrolyte uptake in the blended membrane as com-

pared to the 100 % PVDF. The highest percentages

shown at 90:0:10 blend at 99.1 and 323.4 % for

porosity and electrolyte percentage respectively were

attributed to the absorption nature of cellulose based

membranes. These findings proved that addition of CA

brought about an improvement in membrane proper-

ties. Properties best suited for battery separators.

References

Appetecchi GB (1995) Kinetics and stability of the lithium

electrode in poly (methylmethacrylate)-based gel electro-

lytes. Electrochim Acta 40(8):991–997

Arora P, Zhengming Z (2004) Battery separators. Chem Rev

104(10):419–4462. doi:10.1021/cr020738u

Bauduin G, Boutevin B, Gramain P, Malinova A (1999)

Poly(vinylidene uoride)/poly(vinyl alcohol-co-vinyl ace-

tate) blends: 1. Compatibility Study by differential scan-

ning calorimetry (DSC). Eur Polym J 35:285–292

Cui W-W, Tang D-Y, Gong Z-L (2013a) Electrospun

poly(vinylidene fluoride)/poly(methyl methacrylate) graf-

ted TiO2 composite nanofibrous membrane as polymer

100 0 0 90 10 0 90 5 5 90 0 100

50

100

150

200

250

300

350

PVDF: PMMA: CA membranes

Ele

ctro

lyte

Upt

akte

(%

)

275% 278%

315%323%

Fig. 7 Electrolyte uptake of electrospun membrane

Cellulose

123

electrolyte for lithium-ion batteries. J Power Sources

223:206–213. doi:10.1016/j.jpowsour.2012.09.049

Cui Z, Drioli E, Lee YM (2013b) Recent progress in fluoro-

polymers for membranes. Prog Polym Sci. doi:10.1016/j.

progpolymsci.2013.07.008

Ding Y, Zhang P, Long Z, Jiang Y, Xu F, Di W (2009) The ionic

conductivity and mechanical property of electrospun P

(VdF-HFP)/PMMA membranes for lithium ion batteries.

J Membr Sci 329(1–2):56–59. doi:10.1016/j.memsci.2008.

12.024

Feuillade G, Perche P (1975) Ion-conductive macromolecular

gels and membranes for solid lithium cells. J Appl Elect-

rochem 5(1):63–69. doi:10.1007/BF00625960

Gozdz AS, Plitz I, Pasquier Du A, Red Bank (2002) Use of

electrode-bonded paper separators in non-aqueous slectric

double-layer capacitors and Li-ion batteries. In: Proceedings

of the 201st meeting of the Electrochemical Society, 12–17

Iljima T, Toyogushi Y, Eda N (1985) Quasi-solid organic

electrolytes gelatinized with poly-methyl methacrylate and

their applications for lithium batteries. Electrochem Soc

Jpn 53(8):619–623

Jabbour L, Bongiovanni R, Beneventi D (2013a) Cellulose-

based Li-ion batteries: a review. Cellulose 20:1523–1545.

doi:10.1007/s10570-013-9973-8

Jabbour L, Destro M, Chaussy D, Gerbaldi C, Bodoardo S,

Penazzi N, Beneventi D (2013b) Cellulose/graphite/carbon

fibres composite electrodes for Li-ion batteries. Compos

Sci Technol 87:232–239. doi:10.1016/j.compscitech.2013.

07.029

Kim JR, Choi SW, Jo SM, Lee WS, Kim BC (2005) Charac-

terization and properties of P(VdF-HFP)-based fibrous

polymer electrolyte membrane prepared by electrospin-

ning. J Electrochem Soc 152(2):A295. doi:10.1149/1.

1839531

Kim Y-J, Ahn CH, Lee MB, Choi M-S (2011) Characteristics of

electrospun PVDF/SiO2 composite nanofiber membranes as

polymer electrolyte. Mater Chem Phys 127(1–2):137–142.

doi:10.1016/j.matchemphys.2011.01.046

Kritzer P (2006) Nonwoven support material for improved

separators in Li–polymer batteries. J Power Sources

161(2):1335–1340. doi:10.1016/j.jpowsour.2006.04.142

Lalia BS, Samad YA, Hashaikeh R (2012) Nanocrystalline

cellulose-reinforced composite mats for lithium-ion bat-

teries: electrochemical and thermomechanical perfor-

mance. J Solid State Electrochem 17(3):575–581. doi:10.

1007/s10008-012-1894-1

Lee JM, Nguyen DQ, Lee SB, Kim H, Ahn BS, Lee H, Kim HS

(2010) Cellulose triacetate-based polymer gel electrolytes.

J Appl Polym Sci 115:32–36. doi:10.1002/app.29398

Li X, Cao Q, Wang X, Jiang S, Deng H, Wu N (2011) Prepa-

ration of poly (vinylidene fluoride)/poly (methyl methac-

rylate) membranes by novel electrospinning system for

lithium ion batteries. J Appl Polym Sci 122:2616–2620.

doi:10.1002/app.34401

Liu F, Awanis Hashim N, Yutie Liu MR, Abed Moghareh, Li K

(2011) Progress in the production and modification of

PVDF membranes. J Membr Sci 375(1–2):1–27. doi:10.

1016/j.memsci.2011.03.014

Ma T, Cui Z, Wu Ying, Qin S, Wang H, Yan F, Han N, Li J

(2013) Preparation of PVDF based blend microporous

membranes for lithium ion batteries by thermally induced

phase separation: I. Effect of PMMA on the membrane

formation process and the properties. J Membr Sci

444:213–222. doi:10.1016/j.memsci.2013.05.028

Manuel Stephan A, Nahm KS (2006) Review on composite

polymer electrolytes for lithium batteries. Polymer

47(16):5952–5964. doi:10.1016/j.polymer.2006.05.069

Mu C, Su Y, Sun M, Chen W, Jiang Z (2010) Remarkable

improvement of the performance of poly(vinylidene fluo-

ride) microfiltration membranes by the additive of cellu-

lose acetate. J Membr Sci 350(1–2):293–300. doi:10.1016/

j.memsci.2010.01.004

Padbury R, Zhang X (2011) Lithium–oxygen batteries—limit-

ing factors that affect performance. J Power Sources

196(10):4436–4444. doi:10.1016/j.jpowsour.2011.01.032

Ren Z, Liu Y, Sun K, Zhou X, Zhang N (2009) A microporous

gel electrolyte based on poly(vinylidene fluoride-Co-hex-

afluoropropylene)/fully cyanoethylated cellulose deriva-

tive blend for lithium-ion battery. Electrochim Acta

54(6):1888–1892. doi:10.1016/j.electacta.2008.10.011

Rosso M, Brissot C, Teyssot A, Dolle M, Sannier L, Tarascon

J-M, Bouchet R, Lascaud S (2006) Dendrite short-circuit

and fuse effect on Li/polymer/Li cells. Electrochim Acta

51(25):5334–5340. doi:10.1016/j.electacta.2006.02.004

Samad YA, Asghar A, Hashaikeh R (2013) Electrospun cellu-

lose/PEO fiber mats as a solid polymer electrolytes for Li

ion batteries. Renew Energy 56:90–95. doi:10.1016/j.

renene.2012.09.015

Schneider S, Drujon X, Wittmann JC, Lotz B (2001) Impact of

nucleating agents of PVDF on the crystallization of PVDF/

PMMA blends. Polymer 42(21):8799–8806. doi:10.1016/

S0032-3861(01)00349-4

Subbiah T, Bhat GS, Tock RW, Parameswaran S, Ramkumar SS

(2005) Electrospinning of nanofibers. J Appl Polym Sci

96(2):557–569. doi:10.1002/app.21481

Takemura D, Aihara S, Hamano K, Kise M, Nishimura T,

Urushibata H, Yoshiyasu H (2005) A powder particle size

effect on ceramic powder based separator for lithium

rechargeable battery. J Power Sources 146(1–2):779–783.

doi:10.1016/j.jpowsour.2005.03.159

Tomura H, Inoue T (1992) Light scattering analysis of upper

critical solution temperature behavior in a poly (vinylidene

fluoride)/poly (methyl methacrylate) blend. Macromole-

cules 25:1611–1614

Tseng H-H, Zhuang G-L, Su Y-C (2012) The effect of blending

ratio on the compatibility, morphology, thermal behavior

and pure water permeation of asymmetric CAP/PVDF

membranes. Desalination 284:269–278. doi:10.1016/j.

desal.2011.09.011

Zhang SS (2007) A review on the separators of liquid electrolyte

Li-ion batteries. J Power Sources 164(1):351–364. doi:10.

1016/j.jpowsour.2006.10.065

Zhang S, Xu K, Jow T (2005) An inorganic composite mem-

brane as the separator of Li-ion batteries. J Power Sources

140(2):361–364. doi:10.1016/j.jpowsour.2004.07.034

Zhang LC, Sun X, Hu Z, Yuan CC, Chen CH (2012) Rice paper as

a separator membrane in lithium-ion batteries. J Power

Sources 204:149–154. doi:10.1016/j.jpowsour.2011.12.028

Zheng J, He A, Li J, Han CC (2007) Polymorphism control of

poly(vinylidene fluoride) through electrospinning. Macromol

Rapid Commun 28(22):2159–2162. doi:10.1002/marc.2007

00544

Cellulose

123

Zhou YF, Xie S, Ge XW, Chen CH, Amine K (2004) Prepara-

tion of rechargeable lithium batteries with poly (methyl

methacrylate) based gel polymer electrolyte by in situ c-ray

irradiation-induced polymerization. J Appl Electrochem

34:1119–1125

Zhou W, He J, Cui S, Gao W (2011) Studies of electrospun

cellulose acetate nanofibrous membranes. Open Mater Sci

J 5:51–55

Cellulose

123